Water-insoluble monoazo dyes



United States Patent 7 Claims. of. 260-158) This invention relates to new water-insolube monoazo dyes having the general formula:

in which R denotes an unsubstituted or substituted alkyl radical; R denotes an unsubstituted or substituted alkyl radical; R denotes a hydrogen atom or an unsubstituted or substituted alkyl radical and A denotes an unsubstituted or substituted p-phenylene radical, the dyes being free from ionic water-solubilizing groups such as free sulfonic acid proups or free carboxylic acid groups.

Examples of radicals R are methyl, ethyl, propyl, butyl, pentyl and hexyl. These radicals may contain substituents, such as a cyano, hydroxy, alkoxy, acetylamino or carbalkoxy group or a chlorine or bromine atom.

Radicals R and R may for example contain halogen atoms or nitrile, hydroxyl, alkoxy, acyloxy or carbalkoxy groups as substituents.

Specific examples of the radicals R and R are: methyl, ethyl, propyl, butyl, B-cyanoethyl, p-hydroxyethyl, ,8, dihydroxypropyl, ,B-hydroxy-y-chloropropyl, carbomethoxyethyl, carboethoxyethyl, carbomethoxypropyl, acetoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, methoxyethyl, B-chloroethyl, butan-3-one-1-yl.

The radical 32 has. 7 in the new dyes may be, for example, derived from:

N-ethylaminobenzene, N-butylaminobenzene, N-cyanoethylaminobenzene, N-rnethoxyethyl-3-methylbenzene, N-cyanoethyl-3-chlorobenzene, N,N-diethylaminobenzene, N-ethyl-N-B-hydroxyethylaminobenzene, N-ethyl-N-B-cyanoethylaminobenzene, N-B-hydroxyethyl-N-B-cyanoethylaminobenzene, N-ethyl-N-B-acetoxyethylaminobenzene, N-ethyl-N-fi-methoxyethylaminobenzene, N-18-acetoxyethyl-N-B-cyanoethylaminobenzene, N,N-di- ([i-hyd roxyethyl -aminobenzene, N-B-carbomethoxyethy1-N-B-hydroXyethylaminobenzene, N-p-acetoxyethyl-N-,8-hydroxyethylarninobenzene, N-p-methoxyethyl-N-p-hydroxyethylaminobenzene, N-B-methoxyethyl-N-B-cyanoethylaminobenzene, N-fi-methoxyethyl-N-B-carbomethoxyethylaminobenzene, N-B-methoxyethyl-N-fi-acetoxyethylaminobenzene, N-B-methoxyethyl-N-(butan-3-one-1-yl)-aminobenzene, N-ethyl-N-fl-cyanoethym -methylaminobenzene, N-ethyl-N-B-hydroxyethyl-3-methy1aminobenzene, N-ethyl-N-v-acetylaminopropyl-3-methylaminobenzene, N,N-difl-hydrox-yethyl -3-methylaminobenzene, N-B-cyanoethyl-N-p-hydroxyethyl-3-rnethylaminobenzene,

3,390,145 Patented June 25, 1968 "ice N-B-cyanoethyl-N-B-methoxyethyl-3-methylaminobenzene, N}8-cyanoethyl-N-butyl-3-methylaminobe.nzene, N-fi-hydroxyethyl-N-butyl-3-methylaminobenzene, N-B-chloroethyl-N-butyl-3-methylaminobenzene, N-B-chloroethyl-N-/3-methoxyethyl-3-methylaminobenzene, N,N-di-(fl-hydroxyethyl)-3-chloroaminobenzene, N-B-hydroxyethyl-N-[B-cyanoethyl-3-chloroaminobenzene, N,N-di-(B-hydroxyethyl)-3-acetylaminoaminobenzene, N-fi-hydroxyethyl-N-B-oyanoethyl-3-acetylaminoamino benzene, N,N-di- (B-hydroxyethyl -2-methoxy-5-acetylaminoaminobenzene and N13-hydroxyethyl-N-fi-cyanoethyI-Z-methoxy-S-acetylaminoaminobenzene. For technical reasons, those dyes of the invention are preferred which have the general formula II:

in which Y denotes a hydrogen atom, an alkyl or alkoxy group having one to four carbon atoms, a trifluoromethyl group, an acylamino group having not more than four carbon atoms, or a halogen atom, Z denotes a hydrogen atom or an alkyl or alkox-y group having not more than four carbon atoms and R R and R have the above meanings.

Of the dyes having the formula II, those in turn are particularly suitable in which Y denotes hydrogen, methyl, chloro or acylamino and Z denotes hydrogen. Unsubstituted and substituted ethyl radicals are preferred for the radicals R R and R especially C H.,R and C H R for R and R (R and R denoting nitrile, chloro, hydroxyl, alkoxy with one to four carbon atoms or carbalkoxy with two to four carbon atoms).

The new dyes are eminently suitable, particularly in finely divided form, for dyeing materials, particularly textile materials, such as fibers, filaments, yarn, flock, woven cloth and knitted fabric of acetylcellulose (secondary acetate and triacetate), linear polyesters, for example from terephthalic acid and ethylene glycol or 1,4- dimethylolcyclohexane and polyamides, for example from caprolactam or from hexamethylene diamine and adipic acid.

The dyeings obtained are distinguished by good fastness and good afiinity. In many cases the excellent wet, light, gas fume fading and thermal fastness is particularly noteworthy.

For example the dye in which R is ethyl, R is hydroxyethyl, R is methoxyethyl and Y and Z are both hydrogen is particularly remarkable. It gives excellent ruby dyeings on secondary acetate rayon.

The new dyes may be prepared by methods known per se by condensation or azo coupling, preferably by coupling diazo compounds of amines having the general formula:

0 u R O-C /CNH2 N 111 with compounds having the formula:

n H-A-I1I-R3 1V in which R R R and A have the above meanings.

50 parts of a mixture of anhydrous acetic acid and propionic acid (17:3) is allowed to flow at to C. while stirring into a mixture of 18 parts of nitrosylsulfuric acid having a content of 12.1% of dinitrogen trioxide and 17 parts of concentrated sulfuric acid, and then 13.75 parts of Z-amino-6-carboethoxybenzothiazole is added to this mixture at 0 to 5 C. Then another 50 parts of the said mixture of acetic acid and propionic acid is added and three hours later 2 parts of urea is added with further stirring at 0 to 5 C. The clear diazo solution obtained is allowed to fiow gradually at 0 to 5 C; into a solution of 8.25 parts of N-hydroxyethyl-N-ethyl aniline, parts of water, 6 parts of concentrated hydrochloric acid and 100 parts ,of ice. The reaction mixture is neutralized with a solution of 60 parts of sodium acetate in 300 parts of Water and stirred for twelve hours. The crystalline dye is suction filtered, washed with Water until neutral and dried at C. at subatmospheric pressure. The dye thus obtained dyes acetate rayon bright ruby red shades having very good fastness to gas fume fading and fastness to light.

By using the azo components listed in the following table, instead of the coupling component specified in Example 1, dyes having similar properties are obtained.

Shade of dyeing on Example No. Coupling component Acetate Iolyarnide Polyesterrayon C2I'I5 2 N Red Red Red.

CZH4CN 0,11 3 -N Ruby Red Red.

C2H OC CH CQH OH 4 -N d0 Ruby Red.

' CQILOH CzH OH 5 -N Salmon. Red Red.

C H4CN C I-LOH 6 O-N Rose Red Red czmo O CH C2H4OH 7 N Ruby..- Ruby Red.

C H OCH C2H4OH 8 N .....do ,do Red.

C I'I OCCH O HlCN 9 O-N do do.. Red.

C2H4OCH;

C1H4CN 10 C -N Red Red Red.

CzH4OCCH CQIIAOCHQ l1 N Scarlet. Red Red.

C H4C 02CH CZH4OCH3 12 O-N Ruby Ruby Red.

CzHlOc OOH;

C2H4OCH 13 Q-N Iied Red Red.

C H4C OCH;

'ltose Scarlet Scarlet.

R represents an alkyl radical having 1 to 4 carbon atoms,

Y represents hydrogen, chloro, methyl or acetylamino,

Z represents hydrogen or methoxy,

R represents hydrogen, hydroxy, methoxy or acetyloxy,

and

R represents hydroxy, cyano, acetyloxy, carbomethoxyacetyl, acetylamino or chloro.

3. The dye according to claim 1 and having the formula:

4. The dye according to claim 1 and having the formula:

5. The dye according to claim 1 and having the formula:

s Hallo- /OH;OH2-OH \CH CH 011 N 2' 2 6. The dye according to claim 1 and having the formula:

o S g mom-('1 oHzc'm oH I OHzCHz-OH N NHCOCHa 7. The dye according to claim 1 and having th f mula: I

/CH:CHz- QN I \N/ CHz-CHz-OCOCHs References Cited UNITED STATES PATENTS 3,329,669 7/1967 Sartori 260-1S8 CHARLES B. PARKER, Primary Examiner. D. M. PAP'UGA, Assistant Examiner;

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,390,145 June 25, 1968 Hans Guenter Wippel pears in the above identified It is certified that error ap patent and that said Letters Patent are hereby corrected as shown below:

Column 8, line 43, "3,329,669"

Signed and sealed this 16th day of December 1969.

(SEAL) Attest:

should read 3,329,667

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer 

1. A DYE OF THE FORMULA: 